Sulphonated comb polymers having a selected lithium/sodium ratio and preparations including such polymers

ABSTRACT

Water-soluble and/or water-dispersible comb polymers comprising a polymer main chain and polyester side-arms which contain sulfonic acid groups and which are linked to the polymer main chain via ester groups, wherein said side-arms have been at least partially neutralized by sodium and lithium cations, wherein the molar ratio of lithium to sodium is between 0.1 and 50.

This is a continuation of application Ser. No. 10/090,525, filed Mar. 4,2002, which is a continuation of PCT/EP00/08526, filed Aug. 31, 2000,and also claims the benefit of German Priority Application No. 199 42302.4, filed Sep. 4, 1999, all of which are incorporated by referenceherein in their entirety.

The present invention relates to novel sulphonated comb polymers and topreparations comprising such sulphonated comb polymers. In particular,the present invention relates to hair cosmetic active ingredients andpreparations for setting, shaping, strengthening and improving thestructure of hair.

An attractive hairstyle is nowadays generally regarded as being anindispensable part of a groomed appearance. In this connection, currentfashion trends mean that time and again hairstyles which are consideredchic are those which, for many types of hair, can only be formed ormaintained for a relatively long period using certain setting activeingredients.

For these reasons, for some time use has sometimes been made of haircarecosmetics which are intended to be washed out of the hair againfollowing contact, and sometimes of those which are intended to remainin the hair. The latter can be formulated such that they serve not onlyto care for individual hairs, but also improve the appearance of thehairstyle overall, for example by imparting more fullness to the hair,fixing the hairstyle over a relatively long period or improving itsability to be styled.

The property of fullness is attributed to a hairstyle, for example,when, following treatment, the hair does not lie flat on the scalp andcan be easily styled.

The property of volume is attributed to a hairstyle, for example, when,following treatment, the hair has fullness and bounce.

The property of body is attributed to a hairstyle, for example, when thehair retains its volume even under disruptive external influences.

Setting active ingredients, which are usually polymeric compounds, canbe incorporated into customary hair cleansers or conditioners. In manycases it is, however, advantageous to apply them in the form of specificproducts such as hair setting compositions or hair sprays.

There have recently been a number of developments in the hair cosmeticsfield which have created a need for new types of setting activeingredients and new types of formulation. Many of these developments arebased not on performance disadvantages or shortcomings of knowncompositions, but, for example, on environmental protection viewpoints,legal provisions or other “non-technical” reasons.

For example, efforts are increasing in particular to change over fromcompositions based on volatile organic compounds (abbreviation: VOCs),e.g. alcohols, to water-based compositions.

However, the prior art lacks active ingredients (polymers) andpreparations which conform to the requirements given above. For example,the preparations of the prior art which fix hairstyles generallycomprise constituents (synthetic or natural polymers) which run therisk, in cases where readily volatile organic constituents are partiallyor completely replaced by water, of experiencing significant impairmentof the product properties, which often has to be compensated for byclever formulation. In addition, the fixing preparations of the priorart are frequently distinguished by formulation constituents which haveinsufficient long-term stability and which can only be formulated withdifficulty or in a complex manner, this applying in particular tosilicone derivatives, which are used to improve the flexibility andtactility of the polymer film surface.

It was therefore the object to develop appropriate compositions which,with regard to performance properties, for example spray behaviour anddrying time in the case of hair sprays, satisfy the expectations imposedby the consumer, and at the same time have a reduced content of volatileorganic compounds, without the elementary properties of the polymer filmon the hair, such as, for example, clarity/tranparency, surfacetactility, shine, elasticity and wash-off, being negatively influenced,and where the processability of the formulation constituents is simpleand unproblematical.

It has now been found, and herein lies the basis of the solution to theproblems, that water-soluble and/or water-dispersible comb polymersconsisting of a polymer main chain and polyester side-arms which containsulphonic acid groups and are linked to said polymer main chain viaester groups, which side-arms have been at least partially neutralizedby sodium and lithium counterions, where the molar ratio of lithium tosodium is between 0.1 and 50, preferably between 0.5 and 25, overcome orat least reduce the disadvantages of the prior art.

The comb polymers according to the invention are distinguished both bygood water and alcohol compatibility and by favourable film propertiesand high wetting ability. In addition, they are easy to formulate.

The basic structure of the comb polymers according to the inventionessentially follows the scheme below:

Here, the groups having the designation XXX bonded to one another arethe basic component of a polymer backbone to which molecular groups arebonded via ester functions, said groups having the designation YYY. Themolecular groups YYY are either the complete sulfonic acidgroup-containing polyester side-arms of the comb polymers according tothe invention or else can be other molecular groups.

In this connection, the polymeric main chain of the comb polymers usedaccording to the invention preferably consists of:

a) polymeric aliphatic, cycloaliphatic or aromatic polycarboxylic acidsor derivatives thereof, such as, for example, polyacrylic acid,polymethacrylic acid and esters thereof (esters of the two acids withaliphatic, cycloaliphatic or aromatic alcohols with C₁ to C₂₂), maleicacid, maleic anhydride, fumaric acid and polynorbomenic acid. The numberaverage molecular weights of the polycarboxylic acid used can be between200 and 2,000,000 g/mol, the range 2000–100,000 g/mol being preferablyused.

The polyester side chains are bonded via an ester group which is formedby the reaction of a functional group of the main chain (—COOH in thecase of polycarboxylic acids or —OH in the case of polyalcohols) with acorresponding group of the polyester (OH in the case of polycarboxylicacids and COOH in the case of polyalcohols). It is of course alsopossible for reactive derivatives of the components listed above to bereacted (for example anhydrides, esters, halogen compounds and thelike).

The polyesters used according to the invention can advantageously bedistinguished by the following generic structural formulae:

etc.wherein p and o can be chosen such that the average molecular weights,referred to previously, of the main chain constituents used areachieved.

The polyester side chains according to formula I–III advantageouslyconsist of:

G: an aromatic, aliphatic or cycloaliphatic organyl unit having a carbonnumber of from C₂ to C₂₂ and containing at least two terminal oxygenatoms, or derivatives of a polyglycol of the formHO—[R³—O]_(k)—[R⁴—O]_(m)—H, corresponding to an organyl unit

The radicals R³ and R⁴ are alkylene radicals having a carbon number offrom C₂ to C₂₂, where the two radicals do not necessarily have to bedifferent.

For the coefficients k and m the following applies: k+m≧1, where k and mcan also be chosen such that the average molecular weights, referred topreviously, of the main chain constituents used are achieved.

D: an aromatic, aliphatic or cycloaliphatic organyl unit having a carbonnumber of from C₂ to C₂₂ and containing at least two terminal acylgroups, where combinations of two or more different acid components mayalso be present in the claimed target molecule, for example an organylunit of the scheme

where R^(S) can be aromatic and linear or cyclic, saturated orunsaturated aliphatic bifunctional radicals having carbon numbers offrom C₂ to C₂₂.

T: a compound from the group of the sulphonated aromatic, aliphatic orcycloaliphatic organyl compounds containing at least two terminal acylgroups

R¹: can be lithium and/or sodium as well as, where appropriate, furthercounterions, e.g. potassium, magnesium, calcium, ammonium,monoalkylammonium, dialkylammonium, trialkylammonium ortetraalkylammonium, in which the alkyl positions of the amines are,independently of one another, occupied by C₁ to C₂₂-alkyl radicals and 0to 3 hydroxyl groups.

R²: a molecular moiety chosen from the groups of

-   -   aromatic, aliphatic or cycloaliphatic amino functions: (—NH—R⁵,        —NR⁵ ₂, where R⁵ can be an alkyl or aryl radical with C₁ to C₂₂)    -   aromatic, aliphatic or cycloaliphatic monocarboxylic acid        groups: (—COOR⁶, where R⁶ is an alkyl or aryl radical with C₁ to        C₂₀₀)    -   aromatic, aliphatic or cycloaliphatic organyl radicals bridged        via ether functions:        (—O—R⁵)    -   polyalkoxy compounds bridging via ether functions and of the        form —O—[R⁷—O]_(q)—[R⁸—O]_(r)—Y    -   The radicals R⁷ and R⁸ are advantageously alkyl radicals having        a carbon number of from C₂ to C₂₂, where the two radicals do not        necessarily have to be different. The radical Y can either be        hydrogen or an aliphatic nature with C₁–C₂₂. For the        coefficients q and r the following applies: q+r≧1.    -   mono- or polyethoxylated sulphonated organyl radicals bridging        via ether functions, or preferably alkali metal or alkaline        earth metal salts thereof, such as, for example, advantageously        characterized by the generic structural formula        —(O—CH₂—CH₂)_(s)—SO₃R¹

where s≧1, and where s can also be chosen such that the averagemolecular weights, referred to previously, of the main chainconstituents used are achieved.

The functionality of the components used according to the invention isnot of course limited to the use of OH groups, but also includes COOHend groups, or mixtures of the two, it also being the case here that atleast two COOH groups must be freely present in the molecule. Reactivederivatives such as anhydrides, esters, epoxides or halides can ofcourse also be used.

The number average molecular weights of the comb polymers according tothe invention can advantageously be between 200 and 2,000,000 g/mol,particularly advantageously between 200 and 100,000 g/mol, the range1000–30,000 g/mol being preferably used, very particularlyadvantageously 5000–15,000 g/mol.

The polyesters according to the invention are advantageously prepared byesterifying or transesterifying the parent functional alcohol componentsand diols with the carboxylic acids or suitable derivatives thereof (forexample alkyl esters, halides and the like) in the presence of anesterification catalyst, such as alkali metal hydroxides, carbonates andacetates thereof, alkaline earth metal oxides, hydroxides, carbonatesand acetates, and alkali metal and alkaline earth metal salts of fattyacids having 6 to 22 carbon atoms. Also suitable are titanium compounds,such as titanates, metallic tin and organic tin compounds, such as mono-and dialkyltin derivatives, as esterification catalysts. Theesterification/transesterification is preferably carried out using tinpowder or titanium tetraisopropoxide as catalyst.

The esterification/transesterification is preferably carried out attemperatures of from 120° C. to 280° C. the more readily boilingcondensate (alcohols or water) forming being removed by distillationfrom the condensation product, preferably under reduced pressure up to<0.1 mbar.

Starting materials which can be used for the polyester backbone of combpolymers according to the invention are aliphatic, cycloaliphatic oraromatic polycarboxylic acids or derivatives thereof, such as, forexample, polyacrylic acid, polymethacrylic acid and esters thereof(esters of the two acids with aliphatic, cycloaliphatic or aromaticalcohols with C₁ to C₂₂), maleic acid, maleic anhydride, fumaric acidand polynorbornenic acid. The number average molecular weights of theindividual polycarboxylic acids can be between 200 and 2,000,000 g/mol,the range 2000–100,000 g/mol being preferably used.

Random or block copolymers of the abovementioned class of compound withother vinylic monomers such as, for example, styrene, acrylamide,α-methylstyrene, styrene, N-vinylpyrrolidone, N-vinylcaprolactone,acrylamidopropylenesulphonic acid and the alkali, alkaline earth andammonium salts thereof, MAPTAC (meth-acrylamidopropyltrimethylammoniumchloride), DADMAC, vinylsulphonic acid, vinylphosphonic acid, crotonicacid, vinylacetamide, vinylmethylacetamide, vinylformamide, acrylic acidor methacrylic acid derivatives (for example free acid or ester), oracrylamide derivatives or vinyl acetate can also be used to form thepolymeric main chain.

As the basis for aromatic, aliphatic or cycloaliphatic organyl unitshaving a carbon number of from C₂ to C₂₂ and containing at least twoterminal oxygen atoms, or derivatives of a polyglycol of the formHO—[R³—O]_(k)—[R⁴—O]_(m)—H, it is possible to use bifunctional alcoholcomponents.

Particularly suitable for this purpose are at least difunctionalaromatic, aliphatic or cycloaliphatic alcohols having a carbon numberfrom C₂ to C₂₂ or a polyglycol of the form HO—[R³—O]_(k)—[R⁴—O]_(m)—H.The radicals R³ and R⁴ are alkyl radicals having a carbon number from C₂to C₂₂, where the two radicals can be identical or different. For thecoefficients k and m the following applies: k+m≧1, where k and m canalso be chosen such that the average molecular weights, referred topreviously, of the main chain constituents used are achieved.

It can be of particular advantage to use tri-, tetra- or, generally,polyfunctional alcohol components instead of difunctional alcoholcomponents, advantageously chosen, for example, from the group below:

As the basis for aromatic, aliphatic or cycloaliphatic organyl unitshaving a carbon number of from C₂ to C₂₂ and containing at least twoterminal acyl groups, for example organyl units of the scheme

it is possible to use, for example, aromatic and linear or cyclic,saturated or unsaturated aliphatic carboxylic acids having a carbonnumber of from C₂ to C₂₂ or anhydrides thereof, for example phthalicacid, isophthalic acid, naphthalenedicarboxylic acid,cyclohexanedicarboxylic acid, adipic acid, succinic acid, glutaric acid,pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid.Combinations of two or more different acid components are also possibleas monomer unit in the claimed target molecule.

Suitable sulfonic acid group-containing monomers are sulphonatedaromatic, aliphatic or cycloaliphatic dialcohols, diacids or estersthereof, such as, for example, sulphosuccinic acid, 5-sulphoisophthalicacid or alkali metal or alkaline earth metal salts or mono-, di-, tri-or tetraalkylammonium salts thereof containing C₁ to C₂₂-alkyl radicals.Of the alkali metal salts, particular preference is given to lithium andsodium salts.

Use is also made of aromatic, aliphatic or cycloaliphatic amines with C₁to C₂₂-alkyl or aryl radicals and/or aromatic, aliphatic orcycloaliphatic monocarboxylic acids with C₁ to C₂₀₀-alkyl or arylradicals and/or polyalkoxy compounds of the form—O—[R⁷—O]_(q)—[R⁸—O]_(r)—X, where the radicals R⁷ and R⁸ are alkylradicals, which may be identical or different, are a carbon number offrom C₂ to C₂₂, and the radical X can either by hydrogen or of analiphatic nature with C₁–C₂₂, and the coefficients q and r are: q+r≧1.

Likewise suitable are sulphonated mono- or polyethylene glycols or,preferably, alkali metal or alkaline earth metal salts thereof:(H—(O—CH₂—CH₂)_(s)—SO₃R¹ where s≧1, where s can also be chosen such thatthe average molecular weights, referred to previously, of the main chainconstituents used are achieved.

To prepare the polyesters according to the invention, the alcohols andacids or esters used to form the side chain are advantageously used inthe molar ratios from 1:1 to about 10:1 (1 or 10 parts of di- orpolyol), and the alcohol and water which form, and the excess componentare removed by distillation after condensation has taken place. Alcoholand acid components are preferably present in the target molecule in theapproximate stoichiometric ratio 1:1.

The proportion of acid components containing sulphonic acid radicals is1 to 99 mol %, preferably 10 to 40 mol %, particularly preferably 15 to25 mol %, based on the total amount of carboxylic acids.

The polyesters of the general formula I which contain sulfonic acidgroups have very favourable performance properties if the diolcomponents used are 1,2-propanediol and/or diethylene glycol and/orcyclohexanedimethanol, if the carboxylic acids used are isophthalicacid, also with 1,3-cyclohexanedicarboxylic acid or also with2,6-naphthalenedicarboxylic acid or also with adipic acid, and if thesulpho group-containing radicals used are the sodium and/or lithium saltof 5-sulphoisophthalic acid or the sodium and/or lithium salt ofisethionic acid.

A section from a comb polymer molecule according to the invention isgiven below, a polyacrylic acid chain forming the backbone of the combpolymer molecule. The acid functions have been esterified with polyols,which for their part have been esterified with an acid function ofisophthalic acid molecules. Further polyols from which structuralelements of this polymer molecule are derived are pentaerythritol and1,2-propanediol. The sulphonate group-containing agent from whichstructural elements of the polymer molecule are derived is, for example,the sodium and/or lithium salt of a 5-sulphoisophthalic dialkyl ester.

For reasons of reaction control, which are known to the person skilledin the art, no absolute uniformity of substitution prevails in thetarget polymer; instead, a certain random distribution breadth ofsubstitution is to be assumed. In addition, certain reactive moleculargroups will also be observed crosslinking two or more polymer chains togive a more or less complex network, as the molecular scheme below alsoattempts to show.

The sulfonic acid-containing polyesters to be used according to theinvention are colourless to yellowish, odour-neutral solids. They arereadily soluble in water and alcohols. They can advantageously beincorporated into cosmetic preparations for setting hair.

The comb polymers according to the invention are advantageously preparedby mixing one or more polyfunctional alcohols with a substance whichcontains sulphonic acid groups and at least two carboxyl groups, forexample sodium dimethyl 5-sulphoisophthalate, optionally a furthersubstance containing at least two carboxyl groups, and a polymer, withone or more polycarboxylic acids, for example polyacrylic acid orpolymethacrylic acid, heating the mixture and subjecting it to customarywork-up steps.

In a particular embodiment of the present invention, the water-solubleand/or water-dispersible comb polymers according to the invention,consisting of a polyacrylic acid-containing polymer main chain andsulfonic acid group-containing polyester side-arms, are thereforeincorporated into cosmetic, in particular hair cosmetic, preparations.

For use, the cosmetic and dermatological preparations according to theinvention are applied to the hair in a sufficient amount in the mannercustomary for cosmetics.

The cosmetic and dermatological preparations according to the inventioncan comprise cosmetic auxiliaries, as are customarily used in suchpreparations, e.g. preservatives, bactericides, perfumes, antifoams,dyes, pigments which have a colouring action, thickeners, surface-activesubstances, emulsifiers, emollients, moisturizers and/or humectants,fats, oils, waxes or other customary constituents of a cosmetic ordermatological formulation, such as alcohols, polyols, polymers, foamstabilizers, electrolytes, organic solvents or silicone derivatives.

In cosmetic preparations for setting hair, such as, for example, hairsprays, hair lacquers, setting foams, setting liquids, styling gelsetc., the comb polymers to be used according to the invention maypreferably be used in concentrations of from 0.5 to 30 per cent byweight.

The hair-setting compositions according to the invention can be in theform of hair sprays or foam aerosols, and comprise the additives whichare customary for this purpose and which correspond to the prior art,provided there is corresponding compatibility. These are, for example,further solvents, such as lower polyalcohols and toxicologicallyacceptable ethers and esters thereof, emollients, readily and poorlyvolatile silicones, readily and poorly volatile branched or unbranchedhydrocarbons, emulsifiers, antioxidants, waxes, stabilizers, pHregulators, dyes, bodying agents, antistats, UV absorbers, perfumes,etc.

If the composition according to the invention is to be used as hairspray or foam aerosol, then a propellant is normally added. Customarypropellants are lower alkanes, for example propane, butane or isobutane,dimethyl ether, nitrogen, nitrogen dioxide or carbon dioxide or mixturesof these substances.

In the case of use in mechanical spraying or foaming devices, forexample spray pumps or manual foam pumps or squeeze systems, thepropellant can usually be omitted.

The aqueous preparations according to the invention optionallyadvantageously comprise alcohols, diols or polyols of low carbon number,and ethers thereof, preferably ethanol, isopropanol, propylene glycol,glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether,propylene glycol monomethyl, monoethyl or monobutyl ether, diethyleneglycol monomethyl or monoethyl ether and analogous products, and alsoalcohols of low carbon number, e.g. ethanol, isopropanol,1,2-propanediol, glycerol and, in particular, one or more thickeners,which can be advantageously chosen from the group consisting of silicondioxide, aluminium silicates, polysaccharides and derivatives thereof,e.g. hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose,particularly advantageously from the group of polyacrylates, preferablya polyacrylate from the group of Carbopols, for example Carbopols ofgrades 980, 981, 1382, 2984, 5984, in each case individually or incombination.

In the technical sense, the term gels means: relatively dimensionallystable, readily deformable disperse systems of at least two componentswhich as a rule consist of a—in most cases solid—colloidally dispersedsubstance of long-chain molecular groups (e.g. gelatine, silica,polysaccharides) as the backbone-former and a liquid dispersing agent(e.g. water). The colloidally disperse substance is often referred to asa thickener or gelling agent. It forms a three-dimensional network inthe dispersing agent, it being possible for individual particles presentin colloidal form to be linked to one another more or less firmly viaelectrostatic interaction. The dispersing agent, which surrounds thenetwork, is distinguished by electrostatic affinity for the gellingagent, i.e. a predominantly polar (in particular: hydrophilic) gellingagent preferably gels a polar dispersing agent (in particular: water),whereas a predominantly nonpolar gelling agent preferably gels nonpolardispersing agents.

Strong electrostatic interactions, which are realized, for example, inhydrogen bridge bonds between gelling agent and dispersing agent, butalso between dispersing agent molecules amongst themselves, can lead toa high degree of crosslinking of the dispersing agent as well. Hydrogelscan consist of virtually 100% of water (in addition, for example, toabout 0.2–1.0% of a gelling agent) and have an entirely solidconsistency. The water content is present here in ice-like structuralelements, meaning that gels therefore do justice to the origin of theirname [from Lat. “gelatum”=“frozen” via the alchemistic term “gelatina”(16^(th) century) for the modem term “gelatin”].

Gels according to the invention usually comprise alcohols of low carbonnumber, e.g. ethanol, isopropanol, 1,2-propanediol, glycerol and waterin the presence of a thickener, which in the case of oily-alcoholic gelsis preferably silicon dioxide or an aluminium silicate, and in the caseof aqueous-alcoholic or alcoholic gels is preferably a polyacrylate.

The cosmetic and dermatological preparations according to the inventioncan, for example, also be shampoos, preparations for blow-drying orarranging hair, colouring preparations, or a styling or treatmentlotion.

Preparations according to the invention can optionally advantageously bedistinguished by a content of surfactants. Surfactants are amphiphilicsubstances which are able to dissolve organic nonpolar substances inwater. As a result of their specific molecular structure having at leastone hydrophilic and one hydrophobic molecular moiety, they are able toreduce the surface tension of water, wet the skin, facilitate soilremoval and dissolution, facilitate rinsing and—if desired—controlfoaming.

The hydrophilic moieties of a surfactant molecule are mostly polarfunctional groups, for example —COO⁻, —OSO₃ ²⁻, —SO₃ ⁻, while thehydrophobic moieties are usually nonpolar hydrocarbon radicals.Surfactants are generally classified according to the type and charge ofthe hydrophilic molecular moiety. In this connection, it is possible todifferentiate between four groups:

-   anionic surfactants,-   cationic surfactants,-   amphoteric surfactants and-   nonionic surfactants.

Anionic surfactants usually have, as functional groups, carboxylate,sulphate or sulphonate groups. In aqueous solution, they form negativelycharged organic ions in acidic or neutral media. Cationic surfactantsare characterized almost exclusively by the presence of a quaternaryammonium group. In aqueous solution they form positively charged organicions in acidic or neutral media. Amphoteric surfactants contain bothanionic and cationic groups and accordingly in aqueous solution exhibitthe behaviour of anionic or cationic surfactants depending on the pH. Instrongly acidic media they have a positive charge, and in alkalinemedium a negative charge. By contrast, in the neutral pH range, they arezwitterionic, as the example below serves to illustrate:

RNH₂ ⁺CH₂CH₂COOH X⁻ (at pH = 2) X⁻ = any anion, e.g. Cl⁻ RNH₂⁺CH₂CH₂COO⁻ (at pH = 7) RNHCH₂CH₂COO⁻ B⁺ (at pH = 12) B⁺ = any cation,e.g. Na⁺Polyether chains are typical of nonionic surfactants. Nonionicsurfactants do not form ions in an aqueous medium.A. Anionic SurfactantsAnionic surfactants which can be used advantageously are acylamino acids(and salts thereof), such as

-   1. acyl glutamates, for example sodium acyl glutamate,    di-TEA-palmitoyl aspartate and sodium caprylic/capric glutamate,-   2. acylpeptides, for example palmitoyl-hydrolysed milk protein,    sodium cocoyl-hydrolysed soya protein and sodium/potassium    cocoyl-hydrolysed collagen,-   3. sarcosinates, for example myristoyl sarcosinate, TEA-lauroyl    sarcosinate, sodium lauroyl sarcosinate and sodium cocoyl    sarcosinate,-   4. taurates, for example sodium lauroyl taurate and sodium    methylcocoyl taurate,-   5. acyl lactylates, lauroyl lactylate, caproyl lactylate-   6. alaninates    carboxylic acids and derivatives, such as-   1. carboxylic acids, for example lauric acid, aluminium stearate,    magnesium alkanolate and zinc undecylenate,-   2. ester carboxylic acids, for example calcium stearoyl lactylate,    laureth-6 citrate and sodium PEG-4 lauramide carboxylate,-   3. ether carboxylic acids, for example sodium laureth-13 carboxylate    and sodium PEG-6 cocamide carboxylate,    Phosphoric esters and salts, such as, for example, DEA-oleth-10    phosphate and dilaureth-4 phosphate,    sulphonic acids and salts, such as-   1. acyl isethionates, e.g. sodium/ammoniumcocoyl isethionate,-   2. alkylarylsulphonates,-   3. alkylsulphonates, for example sodium cocomonoglyceride sulphate,    sodium C₁₂₋₁₄-olefin sulphonate, sodium lauryl sulphoacetate and    magnesium PEG-3 cocamide sulphate,-   4. sulphosuccinates, for example dioctyl sodium sulphosuccinate,    disodium laureth sulphosuccinate, disodium lauryl sulphosuccinate    and disodium undecyleneamido-MEA sulphosuccinate and    sulphuric esters, such as-   1. alkyl ether sulphates, for example sodium, ammonium, magnesium,    MIPA, TIPA laureth sulphate, sodium myreth sulphate and sodium    C₁₂₋₁₃ pareth sulphate,-   2. alkyl sulphates, for example sodium, ammonium and TEA lauryl    sulphate.    B. Cationic Surfactants    Cationic surfactants which can optionally be used advantageously are-   1. alkylamines,-   2. alkylimidazoles,-   3. ethoxylated amines and-   4. quaternary surfactants,-   5. ester quats    Quaternary surfactants contain at least one N atom which is    covalently bonded to 4 alkyl or aryl groups. Irrespective of the pH,    this leads to a positive charge. Alkylbetaine,    alkylamidopropylbetaine and alkylamidopropylhydroxysultaine are    advantageous. The cationic surfactants used according to the    invention can also preferably be chosen from the group of quaternary    ammonium compounds, in particular benzyltrialkylammonium chlorides    or bromides, such as, for example, benzyldimethylstearylammonium    chloride, and also alkyltrialkylammonium salts, for example    cetyltrimethylammonium chloride or bromide,    alkyldimethylhydroxyethylammonium chlorides or bromides,    dialkyldimethylammonium chlorides or bromides,    alkylamidoethyltrimethylammonium ether sulphates, alkylpyridinium    salts, for example lauryl- or cetylpyridinium chloride, imidazoline    derivatives and compounds having cationic character, such as amine    oxides, for example alkyldimethylamine oxides or    alkylaminoethyldimethylamine oxides. In particular the use of    cetyltrimethylammonium salts is advantageous.    C. Amphoteric Surfactants    Amphoteric surfactants which can be used advantageously are-   1. acyl/dialkylethylenediamine, for example sodium acyl    amphoacetate, disodium acyl amphodipropionate, disodium alkyl    amphodiacetate, sodium acyl amphohydroxypropylsulphonate, disodium    acyl amphodiacetate and sodium acyl amphopropionate,-   2. N-alkylamino acids, for example aminopropylalkylglutamide,    alkylaminopropionic acid, sodium alkylimidodipropionate and    lauroamphocarboxyglycinate.    D. Nonionic Surfactants    Nonionic surfactants which can be used advantageously are-   1. alcohols,-   2. alkanolamides, such as cocamides MEA/DEA/MIPA,-   3. amine oxides, such as cocoamidopropylamine oxide,-   4. esters which are formed by esterification of carboxylic acids    with ethylene oxide, glycerol, sorbitol or other alcohols,-   5. ethers, for example ethoxylated/propoxylated alcohols,    ethoxylated/propoxylated esters, ethoxylated/propoxylated glycerol    esters, ethoxylated/propoxylated cholesterols,    ethoxylated/propoxylated triglyceride esters,    ethoxylated/propoxylated lanolin, ethoxylated/propoxylated    polysiloxanes, propoxylated POE ethers and alkyl polyglycosides,    such as lauryl glucoside, decyl glycoside and cocoglycoside.-   6. sucrose esters, sucrose ethers-   7 polyglycerol esters, diglycerol esters, monoglycerol esters-   8. methylglucose esters, esters of hydroxy acids

Also advantageous is the use of a combination of anionic and/oramphoteric surfactants with one or more nonionic surfactants.

For the purposes of the present invention, the use of anionic,amphoteric and/or nonionic surfactants is generally preferable over theuse of cationic surfactants.

The cosmetic and dermatological preparations optionally comprise activeingredients and auxiliaries as are customarily used for this type ofpreparation for hair care and hair treatment. Auxiliaries used arepreservatives, surface-active substances, antifoams, thickeners,emulsifiers, fats, oils, waxes, organic solvents, bactericides,perfumes, dyes or pigments, the objective of which is to colour the hairor the cosmetic or dermatological preparation itself, electrolytes, andsubstances to counteract greasiness in hair.

For the purposes of the present invention, the term electrolytes meanswater-soluble alkali metal, ammonium, alkaline earth metal (includingmagnesium) and zinc salts of inorganic anions and any mixtures of suchsalts, when it has to be ensured that these salts are distinguished bypharmaceutical or cosmetic acceptability.

The anions according to the invention are preferably chosen from thegroup of chlorides, sulphates and hydrogensulphates, phosphates,hydrogenphosphates and linear and cyclic oligophosphates, and carbonatesand hydrogencarbonates.

Cosmetic preparations which are shampoos preferably comprise at leastone anionic, nonionic or amphoteric surface-active substance, or elsemixtures of such substances in the aqueous medium and auxiliaries as arecustomarily used therefor. The surface-active substance or the mixturesof these substances can be present in the shampoo in a concentrationbetween 1% by weight and 50% by weight.

A cosmetic preparation in the form of a lotion which is not rinsed out,in particular a lotion for arranging hair, a lotion used during theblow-drying of hair, a styling and treatment lotion, is generally anaqueous, alcoholic or aqueous-alcoholic solution and comprises the combpolymers according to the invention.

The compositions according to the invention optionally comprise theadditives customary in cosmetics, for example perfume, thickeners, dyes,deodorants, antimicrobial substances, refatting agents, complexingagents and sequestering agents, pearlizing agents, plant extracts,vitamins, active ingredients and the like.

The examples below serve to illustrate the present invention withoutlimiting it. Unless stated otherwise, all amounts, proportions andpercentages are based on the weight and the total amount or on the totalweight of the preparations.

(A) PREPARATION EXAMPLES Preparation Example 1

Starting material Mass (g) Isophthalic acid 265.81 5-Sulfoisophthalicmethyl ester, Na salt 100.52 5-Sulfoisophthalic acid, Li salt 22.92Isethionic acid, Na salt 10.96 Polyacrylic acid (M_(n) = 2000 g/mol)3.00 Sodium carbonate 0.60 Titanium tetraisopropoxide 0.601,2-Propanediol 195.40 Diethylene glycol 166.95Preparation Method:

A 2 L four-necked flask fitted with precision-ground stirrer, internalthermometer, gas inlet pipe and distillation bridge is charged with1,2-propanediol, diethylene glycol, 5-sulfoisophthalic methyl ester Nasalt, 5-sulfoisophthalic acid Li salt, sodium carbonate and titaniumtetraisopropoxide, and the mixture is transesterified at 180° C. for 5hours. The methanol and water of reaction which form in the process aredistilled off at atmospheric pressure. The sodium salt of isethionicacid, isophthalic acid and polyacrylic acid are then added to thereaction mixture, which is then rendered thoroughly inert with N₂. Thereaction mixture is then heated slowly to 220° C. and held at thistemperature until no further condensate distills over. Then, over aperiod of 3 hours, starting from atmospheric pressure, the internalpressure of the reaction vessel is reduced to oil pump vacuum. After afurther 60 minutes, N₂ is admitted and the hot polymer melt isdischarged.

Preparation Example 2

Starting material Mol (mmol) 1,3-Cyclohexanedicarboxylic acid 132.80Terephthalic dimethyl ester 95.12 5-Sulfoisophthalic methyl ester, Nasalt 75.20 5-Sulfoisophthalic acid, Li salt 75.20 Polyacrylic acid(M_(n) = 5000 g/mol) 7.00 Sodium carbonate 0.60 Titaniumtetraisopropoxide 0.80 1,2-Propanediol 195.40 Diethylene glycol 166.95Preparation Method:

A 2 L four-necked flask fitted with precision-ground stirrer, internalthermometer, gas inlet tube and distillation bridge is charged with1,2-propanediol, diethylene glycol, 5-sulfoisophthalic methyl ester Nasalt, 5-sulfoisophthalic acid Li salt, sodium carbonate and titaniumtetraisopropoxide, and the mixture is transesterified at 180° C. for 5hours. The methanol and water of reaction which form in the process aredistilled off at atmospheric pressure. The sodium salt of isethionicacid, 1,3-cyclohexanedicarboxylic acid and polyacrylic acid are thenadded to the reaction mixture, which is then rendered thoroughly inertwith N₂. The reaction mixture is then heated slowly to 220° C. and heldat this temperature until no further condensate distills over. Then,over a period of 3 hours, starting from atmospheric pressure, theinternal pressure of the reaction vessel is reduced to oil pump vacuum.After a further 60 minutes, N₂ is admitted and the hot polymer melt isdischarged.

Preparation Example 3

Starting material Mass (g) 2,6-Naphthalenedicarboxylic acid 172.955-Sulfoisophthalic methyl ester, Na salt 55.52 5-Sulfoisophthalic acid,Li salt 97.13 Isophthalic acid 55.00 Poly[acrylic acid-co-methacrylicacid methyl ester] 3.00 M_(n) = 5000 g/mol)* Sodium carbonate 0.60Titanium tetraisopropoxide 0.60 1,2-Propanediol 188.40 Diethylene glycol155.12Preparation Method:

A 2 L four-necked flask fitted with precision-ground stirrer, internalthermometer, gas inlet tube and distillation bridge is charged with1,2-propanediol, diethylene glycol, 5-sulfoisophthalic methyl ester Nasalt, 5-sulfoisophthalic acid Li salt, sodium carbonate and titaniumtetraisopropoxide, and the mixture is transesterified at 180° C. for 5hours. The methanol and water of reaction which form in the process aredistilled off at atmospheric pressure. 2,6-Naphthalenedicarboxylic acid,isophthalic acid and poly[acrylic acid-co-methacrylic acid methyl ester]are then added to the reaction mixture, which is then renderedthoroughly inert with N₂. The reaction mixture is then heated slowly to220° C. and held at this temperature until no further condensatedistills over. Then, over a period of 3 hours, starting from atmosphericpressure, the internal pressure of the reaction vessel is reduced to oilpump vacuum. After a further 75 minutes, N₂ is admitted and the hotpolymer melt is discharged.

Preparation Example 4

Starting material Mol (mmol) Adipic acid 172.95 5-Sulfoisophthalicmethyl ester, Na salt 55.52 5-Sulfoisophthalic acid, Li salt 97.13Isophthalic acid 55.00 Polyacrylic acid (N_(n) = 5000 g/mol) 3.00 Sodiumcarbonate 0.60 Titanium tetraisopropoxide 0.60 Diethylene glycol 400.00Preparation Method:

A 2 L four-necked flask fitted with precision-ground stirrer, internalthermometer, gas inlet tube and distillation bridge is charged withdiethylene glycol, 5-sulfoisophthalic methyl ester Na salt,5-sulfoisophthalic acid Li salt, sodium carbonate, titaniumtetraisopropoxide, isophthalic acid, polyacrylic acid and adipic acid,and the mixture is slowly heated to 200° C. The methanol and water ofreaction which form in the process are distilled off at atmosphericpressure. The mixture is then rendered adequately inert with N₂ and thereaction mixture is slowly heated to 250° C. and maintained at thistemperature until no more condensate distills over. Then, over a periodof 3 hours, starting from atmospheric pressure, the internal pressure ofthe reaction vessel is reduced to oil pump vacuum. After a further 75minutes, N₂ is admitted and the hot polymer melt is discharged.

Preparation Example 5

Starting material Mol (mmol) 1,4-Cyclohexanedicarboxylic acid 172.955-Sulfoisophthalic methyl ester, Na salt 55.52 5-Sulfoisophthalic acid,Li salt 97.13 Isophthalic acid 55.00 Polyacrylic acid (M_(n) = 5000g/mol) 3.00 Cyclohexanedimethanol 150.12 Sodium carbonate 0.60 Titaniumtetraisopropoxide 0.60 Diethylene glycol 400.00Preparation Method:

A 2 L four-necked flask fitted with precision-ground stirrer, internalthermometer, gas inlet tube and distillation bridge is charged withcyclohexanedimethanol, diethylene glycol, 5-sulfoisophthalic methylester Na salt, 5-sulfoisophthalic acid Li salt, sodium carbonate,titanium tetraisopropoxide, isophthalic acid, polyacrylic acid and1,4-cyclohexanedicarboxylic acid, and the mixture is slowly heated to200° C. The methanol and water of reaction which form in the process aredistilled off at atmospheric pressure. The mixture is then renderedsufficiently inert with N₂ and the reaction mixture is slowly heated to250° C. and held at this temperature until no more condensate distillsover. Then, over a period of three hours, starting from atmosphericpressure, the internal pressure of the reaction vessel is reduced to oilpump vacuum. After a further 75 minutes, N₂ is admitted and the hotpolymer melt is discharged.

Preparation Example 6

Starting material Mass (g) Pentaerythritol 7.20 5-Sulfoisophthalic acidmethyl ester, Na salt 15.02 5-Sulfoisophthalic acid, Li salt 140.21Isophthalic acid 55.00 Isethionic acid, Li salt 25.98 Polyacrylic acid(M_(n) = 12,000 g/mol) 3.00 Sodium carbonate 0.60 Titaniumtetraisopropoxide 0.60 1,4-Cyclohexanedimethanol 144.21 Diethyleneglycol 400.00Preparation Method:

A 2 L four-necked flask fitted with precision-ground stirrer, internalthermometer, gas inlet tube and distillation bridge is charged withdiethylene glycol, 5-sulfoisophthalic methyl ester Na salt,5-sulfoisophthalic acid Li salt, sodium carbonate, titaniumtetraisopropoxide, isophthalic acid and pentaerythritol, and the mixtureis slowly heated to 200° C. The methanol and water of reaction whichform during the reaction are distilled off at atmospheric pressure. Thepolyacrylic acid and the isethionic acid Li salt are then added to thereaction mixture. The mixture is then rendered sufficiently inert withN₂ and the reaction mixture is slowly heated to 250° C. and held at thistemperature until no more condensate distills over. Then, over a periodof three hours, starting from atmospheric pressure, the internalpressure of the reaction vessel is reduced to oil pump vacuum. After afurther 75 minutes, N₂ is admitted and the hot polymer melt isdischarged.

(B) FORMULATION EXAMPLES Hair Sprays Examples 1–6

Aerosol hair spray Aerosol hair spray strong hold extra strong hold 1 23 Polyester according to  8.00  8.00 10.00 Preparation Example 1 Ethanol40.00 25.00 25.00 Perfume, care active q.s. q.s. q.s. ingredients, pHregulators, preservatives, solubilizers, corrosion inhibitors Dimethylether 40.00 30.00 30.00 Water, demin. ad 100.00 Aerosol care hairNonaerosol hair spray spray extra strong hold 4 5 6 Polyester accordingto  8.00 10.00 10.00 Preparation Example 2 Ethanol 40.00 — 55.00Perfume, care active q.s. q.s. q.s. ingredients, pH regulators,preservatives, solubilizers, corrosion inhibitors Dimethyl ether 40.00 —— Water, demin. ad 100.00

Setting Foam Examples 7–8

Setting foam Setting foam strong hold extra strong hold 7 8 Polyesteraccording to 8.00 10.00 Preparation Example 3 Cocamidopropylbetaine 0.50 0.50 Perfume, preservatives, pH q.s. q.s. regulators, solubilizers,Propane/butane 8.00  8.00 Water, demin. ad 100.00

Styling Gels Examples 9–10

Styling gel Styling gel strong hold extra strong hold 9 10 Polyesteraccording to 8.00 10.00 Preparation Example 4 Carbomer 0.50  0.50Perfume, preservatives, q.s. q.s. neutralizing agents, solubilizers,Propylene glycol 5.00  5.00 Water, demin. ad 100.00

Styling Shampoos Examples 11–12

Pearlescent styling shampoo 11 12 Polyester according to Preparation5.00 5.00 Example 5 Sodium laureth sulphate 11.00 11.00Cocamidopropylbetaine 2.50 2.50 Glycol distearate 2.00 — Perfume,preservatives, pH regulators, q.s. q.s. solubilizers Dimethiconecopolyol 0.50 0.50 Water, demin. ad 100.00Adjust pH to 6.0

Many modifications and other embodiments of the invention will come tomind to one skilled in the art to which this invention pertains havingthe benefit of the teachings presented in the foregoing descriptions.Therefore, it is to be understood that the invention is not to belimited to the specific embodiments disclosed and that modifications andother embodiments are intended to be included within the scope of theappended claims. Although specific terms are employed herein, they areused in a generic and descriptive sense only and not for purposes oflimitation.

1. A comb polymer that is water-soluble, water-dispersible, or both,comprising a polymer main chain and polyester side-arms which containsulfonic acid groups and which are linked to said polymer main chain viaester groups, wherein said side-arms have been at least partiallyneutralized by sodium and lithium cations, wherein the molar ratio oflithium to sodium is between 0.1 and
 50. 2. The comb polymer accordingto claim 1, wherein the molar ratio of lithium to sodium is between 0.5and
 25. 3. The comb polymer according to claim 1, wherein the polymermain chain comprises at least one polymer selected from the groupconsisting of polyacrylic acid, polymethacrylic acid, esters ofpolyacrylic acid, esters of polymethacrylic acid, polymaleic acid,polymaleic anhydride, and polyfumaric acid.
 4. The comb polymeraccording to claim 1, wherein the polymer main chain comprises at leastone ester of polyacrylic acid or polymethacrylic acid with a C₁ to C₂₂aliphatic, cycloaliphatic or aromatic alcohol.
 5. The comb polymeraccording to claim 1, wherein the polyester side-arms comprise at leastone polyester selected from the group consisting of:

wherein: p and o represent the number of repeating monomer units; G isselected from the group consisting of C₂ to C₂₂ aromatic, aliphatic andcycloaliphatic organyl units containing at least two terminal oxygenatoms and derivatives of a polyglycol of the formulaHO—[R³—O]_(k′)—[R⁴—O]_(m′)—H, corresponding to an organyl unit

wherein R³ and R⁴ are each C₂–C₂₂ alkylene radicals, and are the same ordifferent and k′+m′≧1; D is selected from the group consisting of C₂ toC₂₂ aromatic, aliphatic and cycloaliphatic organyl units containing atleast two terminal acyl groups; T is selected from the group consistingof sulphonated aromatic, aliphatic and cycloaliphatic organyl radicalscontaining at least two terminal acyl groups; at least some of said R¹are lithium and sodium cations, and optionally at least some of said R¹are cations different from lithium and sodium cations; and R² isselected from the group consisting of: aromatic, aliphatic andcycloaliphatic amino functional radicals including a —NH—R⁵ or —NR⁵ ₂group, wherein R⁵ is selected from the group consisting of C₁ to C₂₂alkyl and aryl radicals; aromatic, aliphatic and cycloaliphatic organylradicals bridged via ether functions —O—R⁵, wherein R⁵ is the same asdefined above; mono- or polyethoxylated sulphonated organyl radicalshaving the formula —(O—CH₂—CH₂)_(s)—SO₃R¹, wherein s≧1; and polyalkoxycompounds bridged via ether functions of the formula—O—[R⁷—O]_(q)—[R⁸—O]_(r)—Y, wherein R⁷ and R⁸ are each independentlyselected from the group consisting of C₂ to C₂₂ alkyl radicals and arethe same or different, Y is hydrogen or a C₁–C₂₂ aliphatic radical, andq+r≧1.
 6. The comb polymer according to claim 5, wherein said one ormore additional cations of R¹ are selected from the group consisting ofpotassium, magnesium, calcium, ammonium, monoalkylammonium,dialkylammonium, trialkylammonium and tetraalkylammonium, wherein thealkyl positions of the ammoniums, independently of one another, comprisea C₁ to C₂₂-alkyl radical and 0 to 3 hydroxyl groups.
 7. The combpolymer according to claim 5, wherein D comprises an organyl unit of theformula:

wherein R^(S) is a C₂ to C₂₂ aromatic, linear or cyclic, saturated orunsaturated, aliphatic bifunctional radical.
 8. The comb polymeraccording to claim 7, wherein D is derived from a dicarboxylic acidmonomer selected from the group consisting of phthalic acid, isophthalicacid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, adipicacid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaicacid, sebacic acid, brassylic acid, and combinations thereof.
 9. Thecomb polymer according to claim 1, wherein said polymer has a numberaverage molecular weight from 200 to 2,000,000 g/mol.
 10. The combpolymer according to claim 9, wherein said polymer has a number averagemolecular weight from 200 and 100,000 g/mol.
 11. The comb polymeraccording to claim 10, wherein said polymer has a number averagemolecular weight from 1,000 to 30,000 g/mol.
 12. The comb polymeraccording to claim 11, wherein said polymer has a number averagemolecular weight from 5,000 to 15,000 g/mol.
 13. The comb polymeraccording to claim 5, wherein said polymer has a number averagemolecular weight from 200 to 2,000,000 g/mol.
 14. The comb polymeraccording to claim 13, wherein said polymer has a number averagemolecular weight from 200 and 100,000 g/mol.
 15. The comb polymeraccording to claim 14, wherein said polymer has a number averagemolecular weight from 1,000 to 30,000 g/mol.
 16. The comb polymeraccording to claim 15, wherein said polymer has a number averagemolecular weight from 5,000 to 15,000 g/mol.
 17. A cosmetic preparationcomprising a comb polymer according to claim 1 and one or more cosmeticauxiliaries.
 18. The cosmetic preparation according to claim 17, whereinthe cosmetic preparation is a hair-setting composition, a shampoo, or alotion.
 19. The cosmetic preparation according to claim 18, wherein thecosmetic preparation is a hair-setting composition in the form of aspray, foam aerosol, or gel.
 20. The cosmetic preparation according toclaim 19, wherein the comb polymer is present at a concentration of 0.5to 30 weight percent.